[go: up one dir, main page]

EP0838501B1 - Method and compositions for toughening polyester resins - Google Patents

Method and compositions for toughening polyester resins Download PDF

Info

Publication number
EP0838501B1
EP0838501B1 EP97117911A EP97117911A EP0838501B1 EP 0838501 B1 EP0838501 B1 EP 0838501B1 EP 97117911 A EP97117911 A EP 97117911A EP 97117911 A EP97117911 A EP 97117911A EP 0838501 B1 EP0838501 B1 EP 0838501B1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
ethylene
alkyl
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97117911A
Other languages
German (de)
French (fr)
Other versions
EP0838501A3 (en
EP0838501A2 (en
Inventor
Suzanne Nelsen
Michael Golder
Paul Destio
Mengshi Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0838501A2 publication Critical patent/EP0838501A2/en
Publication of EP0838501A3 publication Critical patent/EP0838501A3/en
Application granted granted Critical
Publication of EP0838501B1 publication Critical patent/EP0838501B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/83—Heating or cooling the cylinders
    • B29C48/832—Heating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates generally to a polyester resins, and specifically to compositions, additives and methods of making such resins, for providing resins with desirable qualities.
  • 4,753,980 refers to polyester compositions comprising 60-97 weight percent of a polyester matrix (e.g., PBT and/or PET) and 3 to 40 weight percent of an ethylene copolymer of the formula E/X/Y, where E is a radical formed from ethylene; Y is selected from the group consisting of glycidyl methacrylate and glycidyl acrylate and X is a radical formed from where R 1 is alkyl of 2 to 8 C, and R 2 is H, CH 3 or C 2 H 5 .
  • These compositions contain an ethylene/acrylic polymer where R 1 of radical X is methyl.
  • This patent refers to ethylene/butylacrylate/glycidyl methacrylate modifiers as superior to ethylene/methacrylate/glycidyl methacrylate modifiers at lower temperatures.
  • US Patent No. 5,175,204 refers to thermoplastic resin compositions which comprise an aromatic polyester and 1 to 50% by weight of a multi-phase structure thermoplastic polyester which is a graft copolymer of 5 to 95% by weight of epoxy group-containing ethylene copolymer and 95-5% by weight of a vinyl polymer or copolymer obtained from at least one vinyl monomer.
  • compositions of the prior art are used as materials for industrial parts, electrical and electronic machine parts, automobiles parts and the like. See, also, U. S. Patent Nos. 4,140,670; 3,368,995; Re. 32,334; 4,499,239; 4,694,042; 5,407,706 and 5,543,464, among others.
  • polyester based resins which have the improved qualities of toughness, i.e., resistance to impact, as well as melt flow properties enabling the use thereof in molded forms.
  • the present invention provides a polyester composition having improved characteristics of impact resistance comprising:
  • the invention provides the acrylic modifier composition comprising:
  • the invention provides an article of manufacture molded from the polyester composition above-described.
  • the invention provides a method for increasing the strength and impact resistance of polyester resins comprising adding to a polyester resin a modifier composition as described above.
  • the method includes the steps of
  • the final step involves physically reducing the size of the solid polyester composition, i.e., pelletization.
  • the present invention provides a novel impact modifier composition which, when added to certain polyester compositions which can be molded into articles such as automobile parts, etc., increases the impact resistance of such articles, i.e., toughens such compositions.
  • the modifier compositions of this invention enable the provision of a polyester composition or resin characterized by increased impact resistance with minimal effect upon the solvent resistance of polyester compositions.
  • the resulting molded article from the polyester compositions of this invention also have relatively high elongation at break and a good flex modulus.
  • acrylic modifier composition or “impact modifier composition” refers to a copolymer/terpolymer two-component composition described in detail below.
  • polyester resin refers to a polyester, or blend thereof with a minor amount of additives, not including the flame retardant composition or reinforcing agents or fillers, as defined below.
  • polyester composition or “total composition” refers to a novel composition of the invention which contains a polyester resin, the impact modifier composition of this invention, and optionally includes flame retardants and reinforcing agents or fillers, as described in detail below.
  • One aspect of this invention is a novel impact modifier composition for addition to polyester resins or compositions, which are intended to be molded at high temperatures into industrially desired, impact resistant and hydrolysis resistant articles.
  • Such novel impact modifier compositions are formulated to contain two components, a copolymer and a terpolymer. Each component may form between 10 to about 90% of the modifier composition.
  • the copolymer component is either an ethylene/alkyl acrylate co-polymer or an ethylene/alkyl methacrylate copolymer.
  • the alkyl component of the ' acrylate or methacrylate polymer in either copolymer has desirably between 1 to 10 carbon atoms.
  • the alkyl acrylate or methacrylate polymer of the copolymer is a methyl acrylate or methyl methacrylate.
  • the copolymer comprises at least about 30% by weight of the alkyl acrylate or alkyl methacrylate, with the balance being the ethylene polymer.
  • Suitable commercially available copolymers are ethylene/methyl acrylate copolymers sold under the tradenames LOTRYL 29MA03 [Elf Atochem]; and other copolymers sold as PRIMACOR 1420, 1430, 1410-XT or 5980 [Dow Chemical]; EMAC SP 2205 and 2207 [Chevron Chemical Co.]; the NUCREL product line [DuPont]; and OPTEMA TC-111 [Exxon Chemical], among others.
  • the terpolymer component of the modifier composition is selected from an ethylene/alkylacrylate/glycidyl methacrylate; an ethylene/alkyl acrylate/glycidyl acrylate; an ethylene/alkyl methacrylate/glycidyl acrylate; and an ethylene/alkyl methacrylate/glycidyl methacrylate.
  • the alkyl component of the acrylate or methacrylate polymer in the terpolymer desirably contains between 1 to 10 carbon atoms.
  • the alkyl acrylate or methacrylate polymer of the terpolymer is a methyl acrylate or methyl methacrylate.
  • the terpolymer comprises between about 1 to about 15% by weight of the glycidyl acrylate or glycidyl methacrylate, and between about 1% to about 40% by weight of the alkyl acrylate or alkyl methacrylate, with the balance being the ethylene units.
  • M n - 10,000 to - 70,000
  • Suitable, commercially available terpolymers include an ethylene/methyl acrylate/glycidyl methacrylate terpolymer sold under the tradenames LOTADER AX8900, AX8920, AX8660, AX8850, AX8870, AX8840 [Elf Atochem],
  • the copolymer and terpolymer components of the modifier composition are characterized by a uniform structure (see Figs. 1A and 1B). Unlike other impact modifiers of the art, these elastomers have no multi-phase structure.
  • the total amount of an impact modifier composition as defined above forms at least 10% of the total composition.
  • the impact modifier compositions may form 20% of the total composition in other embodiments and in certain applications, may form up to 50% by weight of the total polyester compositions.
  • Advantages of the modifier compositions of this invention include providing an acceptable melt viscosity to the total polyester composition. In practical terms, such modifier compositions are also cost-effective compared to other modifiers of the prior art.
  • polyester compositions are thus provided which incorporate the impact modifier compositions described above.
  • such polyester compositions are defined as a polyester composition having improved characteristics of impact resistance and containing the following components:
  • the components (b) and (c) of the polyester composition form the impact modifier composition of the invention.
  • the total amount of the impact modifier composition in the total composition i.e., components (b) and (c)
  • the total amount of the impact modifier composition in the polyester composition does not exceed 40% by weight of the total weight of the composition described above.
  • the total amount of the impact modifier composition in the polyester composition does not exceed 30% by weight of the total weight of the polyester composition.
  • the total amount of the impact modifier composition in the polyester composition does not exceed 20% by weight of the total weight of the polyester composition.
  • the polyester composition can employ any number of thermoplastic polyesters known to be amenable to molding to prepare parts. Such polymers should have a suitable stability to the molding conditions as is well known to those of skill in the art.
  • a suitable polyester may be selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly(ethylene-2,6-naphthalate) (PEN), polyethylene naphthalate bibenzoate (PENBB), poly (1,4-cyclohexanedimethanol terephthalate) (PCT), polypropylene terephthalate (PPT), polybutylene naphthalate (PBN), and liquid crystal polymers (LCPs) such as, for example the VECTRA® brand LCP (Hoechst Celanese Corporation, Somerville, NJ).
  • VECTRA® brand LCP Hoechst Celanese Corporation, Somerville, NJ.
  • polyesters are copolyesters, for example, poly(1,4-cyclohexylene dimethylene terephthalate-coisophthalate), poly(ethylene terephthalate-co-ethylene naphthalate (PETN), and the like.
  • PET and PBT are the most preferred due to their large availability as well as the fact that molding of such resins are well-known in the industry.
  • Blends of the above-listed polyesters may also be suitable for polyester compositions of this invention, including preferably blends of two of such polyesters. Blends of three or more polyesters can be used. Such two component blends are formed by a ratio of between about 5 to 50 % by weight of the total blend. For example, a preferred blend useful in this invention is a ratio of between 5 to about 25% PET and about 75 to about 95% PBT, absent other ingredients.
  • polyester resins or resin blends can contain minor amounts of other polymeric materials, such as polycarbonates, polyphenylene sulfide, polyarylate, polyamide and the like and mixtures thereof.
  • polyesters or co-polyesters are characterized by inherent viscosities of at least 0.4 as measured by ASTM D-2857, and no higher than about 1.4.
  • the modifier composition components (b) and (c) of this invention are very useful with PET alone.
  • additives known to the art. Some of them include, for example, antioxidants, stabilizers, lubricants, nucleating agents, colorants, mold release agents, ultraviolet light stabilizers, and the like. Examples of suitable antioxidants include phosphites. Examples of suitable stabilizers include bis-phenol A based epoxy. Examples of suitable lubricants include olefinic waxes. Examples of suitable nucleating agents include sodium salts. Additives which improve physical properties can also be employed including those which improve tensile strength or the other physical characteristics desirable in such resins. Some of these characteristics are listed in Table 1 below. These additives are present in relatively minor amounts and do not unduly affect the desired characteristics of the finished products. Generally, the additives are present in an amount of between about 1 to about 5% of the total composition.
  • a separate and optional component of the polyester composition is a flame retardant composition or package used at a conventional level.
  • flame retardant compositions include a bromine containing compound (such as brominated polycarbonate, decabromodiphenyloxide, brominated acrylic, brominated polystyrene, etc.).
  • a bromine containing compound such as brominated polycarbonate, decabromodiphenyloxide, brominated acrylic, brominated polystyrene, etc.
  • Such compounds are available commercially, such as from Ethyl Chemical Corp., Great Lakes Chemical Corp., Dead Sea Bromine Co., etc.
  • a synergist typically e.g., antimony oxide, zinc oxide, and sodium antimonate, among others known to the art.
  • a third component of the flame retardant composition is a drip suppressant, such as asbestos, teflon and the like.
  • Suitable flame retardant compositions are known to the art and the selection of the components thereof does not limit the present invention. If a flame retardant composition is present in the polyester composition of this invention, it is present in a percentage by weight of the total composition of between 0 to about 20%.
  • the total polyester composition may include reinforcing agents or fillers.
  • such reinforcing agents or fillers may be present in the total composition between about 0 to about 50% by weight of the total composition.
  • Thermally stable reinforcing agents or reinforcing fibers used in the invention may be any such agents or fibers which are thermally stable at the conditions normally used in the production of products from polyester molding compositions.
  • Suitable reinforcing agents include, for example, glass fiber, asbestos fiber, carbon fiber, ceramic fiber, fibrous potassium titanate, iron whiskers, and the like. Glass is the most preferred. While fiber is the most preferred form for the reinforcing agent, other suitable forms may also be employed in the practice of the invention. Where reinforcing fibers are used, such fibers should normally have diameters between about 5 and about 30 microns, typically from 10-21 ⁇ m, and preferably from 11-16 ⁇ m. Aspect ratios (ratio of length of fiber to diameter of fiber) are desirably at least about 5.
  • the reinforcing fiber typically has a length of generally from 1-10 mm, preferably from 2-6 mm and more preferably from 3-5 mm. Glass fibers, where used, preferably have diameters between about 10 and about 15 microns and aspect ratios of at least about 20.
  • the reinforcing agent/fiber is employed in the polyester composition generally in the range of about 3 to about 50 weight percent based on total weight of the total polyester composition, typically 10-35 weight percent, and preferably 10-30 weight percent.
  • the use of such reinforcing agents/fibers improves substantially such physical properties as tensile strength, flexural strength, flexural modulus and heat distortion temperature of the polyester composition.
  • Glass or other fibers/agents for use in the invention may be manufactured and incorporated into the composition in any suitable manner, such as by separate extrusion blending with the polyester resin, extrusion blending with other ingredients of the compositions of the invention or incorporating into the resin or polyester composition during injection molding of products from the polyester composition.
  • Suitable fillers include, but are not limited to, mica, talcum, clay, titanium dioxide and the like. There may be variants within the same filler type such as, for example, the muscovite type mica (supplied by KMG, Inc.), the phlogopite type mica (Suzorite, Inc.) and the like.
  • the size of the filler particles is in the general range of 20-500 ⁇ m, typically in the range 30-100 ⁇ m and preferably 40-60 ⁇ m.
  • the filler is employed in the polyester composition, generally in the range 5-35 weight percent, typically 7-25 weight percent, and preferably 10-20 weight percent.
  • a polyester composition of the present invention contains about 61.5% by weight of the total composition of PET with about 3.5% additives. About 16% by weight of the total composition is the copolymer ethylene/methyl acrylate. About 4% by weight of the total composition is the terpolymer ethylene/methyl acrylate/glycidyl methacrylate. Finally, about 15% by weight of the total composition is fiberglass. This composition is characterized by a notched Izod impact strength of about 186.8 J/m (3.5 ft-lb/in).
  • polyester compositions falling within this description can be readily prepared by resort to the teachings herein.
  • Useful compositions may have a variety of characteristics, depending on the use to which the molding polyester composition is put.
  • the primary characteristic of the composition is a good notched or unnotched Izod impact strength (ASTM D-256). Generally, the higher the Izod measurement, the better.
  • polyester compositions of this invention are useful in the preparation of molded articles of manufacture, including without limitation, automobile panels, automobile parts, industrial plumbing and other construction parts.
  • the polyester compositions of this invention are prepared by resorting to conventional methods.
  • the impact modifier composition may be prepared by first dry mixing the components.
  • the co-polymers and terpolymers may simply be blended or dry mixed at any convenient speeds and at room temperature.
  • the impact modifier composition components may be combined and sold as a physical or mechanical blend for addition to the polyester resin during manufacture of the polyester composition.
  • the individual components of the modifier composition may be dry mixed directly with the components of the polyester resin.
  • the other ingredients of the polyester composition may also be added.
  • the reinforcing fibers may be intimately blended into the polyester resin by any suitable means such as by dry blending or melt blending, blending in extruders, heated rolls or other types of mixers, etc. Conventional master batching techniques may also be used. The same considerations apply to addition of the other essential or optional ingredients of the composition of the invention, including specifically an inert filler of low aspect ratio, the reinforcing agents, the polyester compositions, etc. Suitable blending and molding techniques are well known in the art and need not be described in detail herein.
  • the extrusion may be carried out in a suitable extruder such as for example a twin screw extruder with down-stream feeding capability.
  • a suitable extruder such as for example a twin screw extruder with down-stream feeding capability.
  • Many such extruders are commercially available such as, for example, the 40 mm Werner Pleiderer twin screw extruder.
  • the extruder may be fed with the resin and additives stated above at the main feeder while the glass is fed downstream.
  • the machine temperature is kept at a suitable level above the melting point of the selected polyester(s). For PET, for example, the temperature may range 260-300°C.
  • the material is compounded and then extruded into a suitable shape such as, for example, pellets. The pellets may then be injection molded into suitable parts.
  • the polyester composition of the invention is compounded by dry blending the polyester resin, the reinforcing agent and/or filler and the impact modifier composition, followed by melt mixing in an extruder at a temperature which exceeds the melting point of the polyester resin, i.e., with barrel temperatures between about 260 and about 300°C.
  • injection molding is preferred.
  • barrel temperatures between about 260 and 290°C are preferred.
  • the molding polyester composition of the invention is formed by extrusion and pelletized. Products of the invention are then produced by injection molding the pelletized extrudate.
  • the individual components of the modifier composition may be added to the extruder separately from the polyester resin and other components of the polyester composition.
  • the components may be blended into the molten mixture prior to cooling.
  • polyester compositions of this invention containing the impact modifier compositions when obtained by the end user, may be dried by any convenient method, remelted and molded into a number of industrially useful products, as described above.
  • COMPONENT A represents a commercial composition of ethylene ethylacrylate (Union Carbide).
  • COMPONENT B represents a terpolymer of ethylene/methyl methacrylate /glycidyl methacrylate with a high (i.e., greater than 5% by weight) epoxy (glycidyl) level (Elf Atochem).
  • COMPONENT C is a terpolymer of ethylene/methyl methacrylate /glycidyl methacrylate with a low (i.e., less than 5% by weight) epoxy (glycidyl) level (Elf Atochem).
  • COMPONENT D is a 70%/30% ethylene/methyl acrylate copolymer with a melt index lower than 5. Suitable copolymers are marketed by Elf Atochem.
  • Component C when raised from 5% (Table 1) to 20% by weight (Table 2) as the impact modifier, produced an increase in notched Izod measurement from 75.8 to 144.2 J/m (1.42 to 2.70 ft-lb/n), and in unnotched Izod from 363 to 769 J/m (6.8 to 14.4 ft-lb/n).
  • Component D alone as impact modifier when raised from 5% (Table 1) to 20% by weight (Table 2) in the composition produced no or little appreciable change in notched Izod (66.7 to 69.4 J/m) (1.25 to 1.3 ft-lb/in) or unnotched Izod measurement (347 to 427 J/m) (6.5 to 8.0 ft-lb/in).
  • Components B and C are good impact modifiers when used alone, but Component D is not an effective impact modifier when used alone in polyester.
  • an impact modifier composition containing Component B and Component D produced the best results in the PET composition of the experiment.
  • the good results appear independent of the ratio of the two components to each other (see Table 2).
  • the best overall results are provided by the impact modifier composition containing 4% terpolymer B and 16% copolymer D.
  • Another good impact modifier composition contains 14% by weight terpolymer B and 6% by weight co-polymer D.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Epoxy Resins (AREA)

Description

    Field of the Invention
  • The present invention relates generally to a polyester resins, and specifically to compositions, additives and methods of making such resins, for providing resins with desirable qualities.
    • Background of the Invention
  • In general, the use of olefinic impact modifiers in polyester compositions to provide molded articles having improved mechanical properties, particularly improved impact resistance has been well known. US Patent No. 4,172,859 claims polyester blends including ethylene/methyl acrylate/glycidyl acrylate polymers. US Patent No. 4,753,980 refers to polyester compositions comprising 60-97 weight percent of a polyester matrix (e.g., PBT and/or PET) and 3 to 40 weight percent of an ethylene copolymer of the formula E/X/Y, where E is a radical formed from ethylene; Y is selected from the group consisting of glycidyl methacrylate and glycidyl acrylate and X is a radical formed from
    Figure 00020001
    where R1 is alkyl of 2 to 8 C, and R2 is H, CH3 or C2H5. These compositions contain an ethylene/acrylic polymer where R1 of radical X is methyl. This patent refers to ethylene/butylacrylate/glycidyl methacrylate modifiers as superior to ethylene/methacrylate/glycidyl methacrylate modifiers at lower temperatures.
  • US Patent No. 5,175,204 refers to thermoplastic resin compositions which comprise an aromatic polyester and 1 to 50% by weight of a multi-phase structure thermoplastic polyester which is a graft copolymer of 5 to 95% by weight of epoxy group-containing ethylene copolymer and 95-5% by weight of a vinyl polymer or copolymer obtained from at least one vinyl monomer.
  • These, and other compositions of the prior art are used as materials for industrial parts, electrical and electronic machine parts, automobiles parts and the like. See, also, U. S. Patent Nos. 4,140,670; 3,368,995; Re. 32,334; 4,499,239; 4,694,042; 5,407,706 and 5,543,464, among others.
  • There remains a need in the art for polyester based resins which have the improved qualities of toughness, i.e., resistance to impact, as well as melt flow properties enabling the use thereof in molded forms.
    • Summary of the Invention
  • In one aspect, the present invention provides a polyester composition having improved characteristics of impact resistance comprising:
  • (a) between 40% and 90% by weight of the total composition of a polyester resin containing a polyester and between 1% and 5% by weight of the total composition of additives;
  • (b) between 5% to 25% by weight of the total composition of a component selected from the group consisting of an ethylene alkyl acrylate copolymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10;
  • (c) between 5% to 25% by weight of the total composition of a component selected from the terpolymer group consisting of ethylene/alkylacrylate/glycidyl methacrylate; ethylene/alkyi acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate, wherein said alkyl is C1 to C10;
  • (d) from 3% to 50% by weight of the total composition of a reinforcing agent; and
  • (e) from 0% to 20% by weight of the total composition of a flame retardant composition.
  • In another aspect, the invention provides the acrylic modifier composition comprising:
  • (a) between 10% to 90% by weight of a first component selected from the group consisting of an ethylene alkyl acrylate co-polymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10; and
  • (b) between 10% to 90% by weight of a second component selected from the terpolymer group consisting of ethylene/alkylacrylate/ glycidyl methacrylate; ethylene/alkyl acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate,
    • wherein said alkyl is C1 to C10; for improving impact resistance of reinforced polyester compositions.
  • In still another aspect, the invention provides an article of manufacture molded from the polyester composition above-described.
  • In yet a further aspect, the invention provides a method for increasing the strength and impact resistance of polyester resins comprising adding to a polyester resin a modifier composition as described above.
  • In still a further aspect, the method includes the steps of
  • (a) melting between 40% and 90% by weight of the total composition of a polyester resin and between 1% and 5% by weight of the total composition of additives at a temperature in excess of the melting temperature of said polyester in an extruder;
  • (b) adding to the composition of step (a) a modifier composition comprising between 10% to 90% by weight of a first component selected from the group consisting of an ethylene alkyl acrylate copolymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10; and between 10% to 90% by weight of a second component selected from the terpolymer group consisting of ethylene/alkylacrylate/glycidyl methacrylate; ethylene/alkyl acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate, wherein said alkyl is C1 to C10;
  • (c) adding to the composition of step (b) a reinforcing agent; and/or
  • (d) adding to the composition of step (c) a reinforcing agent;
  • (e) extruding the molten composition resulting from steps (a) through (d) from said extruding apparatus, wherein said composition extrudes as an intimate mixture;
  • (f) subjecting said mixture of step (e) to means to decrease the temperature thereof and solidify said mixture; and
  • (g) subjecting said solid composition of step (f) to means to reduce its size.
  • The final step involves physically reducing the size of the solid polyester composition, i.e., pelletization.
  • Other aspects and advantages of the present invention are described in the detailed description below and in the claims.
    • Brief Description of the Drawings
  • Fig. 1A is a scanning electron micrograph (SEM) of a terpolymer useful in this invention, i.e., an ethylene/methylacrylate/glycidylmethacrylate terpolymer. Magnification is 2000x. This terpolymer is a homogeneous composition. It is not multi-phase, nor particulate.
  • Fig. 1B is a SEM of an ethylene/methylacrylate copolymer useful in this invention. Magnification is 2000x. This copolymer is a homogeneous composition. It is not multi-phase, nor particulate.
  • Fig. 2 is a SEM of a polyester composition containing PET with fiberglass and 5% by weight of an ethylene/ethylacrylate (EEA) copolymer. This composition demonstrates poor adhesion of impact modifier (EEA copolymer) used to the PET matrix, and an average particle size greater than 1 micron.
  • Fig. 3 is a SEM of a polyester composition containing PET with fiberglass and 20% by weight of an ethylene/methylacrylate/glycidylmethacrylate terpolymer. This SEM demonstrates good adhesion to the PET matrix, and an average particle size of less than one micron.
  • Fig. 4 is a SEM of a polyester composition of PET with fiberglass and 20% by weight of an ethylene/methylacrylate copolymer. This SEM shows elongated particles with a size greater than one micron, and poor adhesion to PET.
  • Fig. 5 is a SEM of a polyester composition according to the invention containing PET with fiberglass and an impact modifier of 4% by weight of an ethylene/methylacrylate/glycidylmethacrylate terpolymer and 16% by weight of an ethylene/methylacrylate copolymer. This SEM shows an average particle size of about 1 micron, a spherical particle shape and good adhesion to the polyester.
    • Detailed Description of the Invention
  • The present invention provides a novel impact modifier composition which, when added to certain polyester compositions which can be molded into articles such as automobile parts, etc., increases the impact resistance of such articles, i.e., toughens such compositions. Particularly the modifier compositions of this invention enable the provision of a polyester composition or resin characterized by increased impact resistance with minimal effect upon the solvent resistance of polyester compositions. The resulting molded article from the polyester compositions of this invention also have relatively high elongation at break and a good flex modulus.
  • As used herein, the term "acrylic modifier composition" or "impact modifier composition" refers to a copolymer/terpolymer two-component composition described in detail below.
  • As used herein, the term "polyester resin", refers to a polyester, or blend thereof with a minor amount of additives, not including the flame retardant composition or reinforcing agents or fillers, as defined below.
  • As used herein, the term "polyester composition" or "total composition" refers to a novel composition of the invention which contains a polyester resin, the impact modifier composition of this invention, and optionally includes flame retardants and reinforcing agents or fillers, as described in detail below.
    • I. Impact Modifier Composition
  • One aspect of this invention is a novel impact modifier composition for addition to polyester resins or compositions, which are intended to be molded at high temperatures into industrially desired, impact resistant and hydrolysis resistant articles. Such novel impact modifier compositions are formulated to contain two components, a copolymer and a terpolymer. Each component may form between 10 to about 90% of the modifier composition.
  • The copolymer component is either an ethylene/alkyl acrylate co-polymer or an ethylene/alkyl methacrylate copolymer. The alkyl component of the ' acrylate or methacrylate polymer in either copolymer has desirably between 1 to 10 carbon atoms. Preferably, the alkyl acrylate or methacrylate polymer of the copolymer is a methyl acrylate or methyl methacrylate. Preferably, the copolymer comprises at least about 30% by weight of the alkyl acrylate or alkyl methacrylate, with the balance being the ethylene polymer. A variety of such copolymers having suitable molecular weight ranges (Mn = -15,000 to -50,000) or suitable viscosities (melt index of 1-300 g/10 minutes at 190°C/2.16 kg) are commercially available. Suitable commercially available copolymers are ethylene/methyl acrylate copolymers sold under the tradenames LOTRYL 29MA03 [Elf Atochem]; and other copolymers sold as PRIMACOR 1420, 1430, 1410-XT or 5980 [Dow Chemical]; EMAC SP 2205 and 2207 [Chevron Chemical Co.]; the NUCREL product line [DuPont]; and OPTEMA TC-111 [Exxon Chemical], among others.
  • The terpolymer component of the modifier composition is selected from an ethylene/alkylacrylate/glycidyl methacrylate; an ethylene/alkyl acrylate/glycidyl acrylate; an ethylene/alkyl methacrylate/glycidyl acrylate; and an ethylene/alkyl methacrylate/glycidyl methacrylate. The alkyl component of the acrylate or methacrylate polymer in the terpolymer desirably contains between 1 to 10 carbon atoms. Preferably, the alkyl acrylate or methacrylate polymer of the terpolymer is a methyl acrylate or methyl methacrylate. Preferably the terpolymer comprises between about 1 to about 15% by weight of the glycidyl acrylate or glycidyl methacrylate, and between about 1% to about 40% by weight of the alkyl acrylate or alkyl methacrylate, with the balance being the ethylene units. A variety of such terpolymers having suitable molecular weight ranges (Mn = -10,000 to -70,000) are commercially available. Suitable, commercially available terpolymers include an ethylene/methyl acrylate/glycidyl methacrylate terpolymer sold under the tradenames LOTADER AX8900, AX8920, AX8660, AX8850, AX8870, AX8840 [Elf Atochem],
  • The copolymer and terpolymer components of the modifier composition are characterized by a uniform structure (see Figs. 1A and 1B). Unlike other impact modifiers of the art, these elastomers have no multi-phase structure.
  • As will be clear to one of skill in the art, from a review of this specification and particularly the examples hereof, a variety of such modifier compositions can be designed to fall within the parameters of this disclosure.
  • In polyester compositions of this invention, the total amount of an impact modifier composition as defined above forms at least 10% of the total composition. The impact modifier compositions may form 20% of the total composition in other embodiments and in certain applications, may form up to 50% by weight of the total polyester compositions. Advantages of the modifier compositions of this invention include providing an acceptable melt viscosity to the total polyester composition. In practical terms, such modifier compositions are also cost-effective compared to other modifiers of the prior art.
    • II. Polyester Compositions
  • Polyester compositions are thus provided which incorporate the impact modifier compositions described above. In general, such polyester compositions are defined as a polyester composition having improved characteristics of impact resistance and containing the following components:
  • (a) between about 40 and about 90% by weight of the total composition of a polyester resin containing a polyester and minor amounts of additives;
  • (b) between about 5 to about 25% by weight of the total composition of a component selected from the group consisting of the co-polymers described above;
  • (c) between about 5 to about 25% by weight of the total composition of a terpolymer as defined above,
  • (d) from 0 to about 50% by weight of the total composition of a reinforcing agent; and
  • (e) from 0 to about 20% by weight of the total composition of a flame retardant composition.
  • As is clear from the above description of the impact modifier composition, the components (b) and (c) of the polyester composition form the impact modifier composition of the invention. Desirably, then, the total amount of the impact modifier composition in the total composition (i.e., components (b) and (c)) does not exceed 40% by weight of the total weight of the composition described above. Also preferably the total amount of the impact modifier composition in the polyester composition does not exceed 30% by weight of the total weight of the polyester composition. In another embodiment, the total amount of the impact modifier composition in the polyester composition does not exceed 20% by weight of the total weight of the polyester composition.
  • According to this embodiment of the invention, the polyester composition can employ any number of thermoplastic polyesters known to be amenable to molding to prepare parts. Such polymers should have a suitable stability to the molding conditions as is well known to those of skill in the art. A suitable polyester may be selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly(ethylene-2,6-naphthalate) (PEN), polyethylene naphthalate bibenzoate (PENBB), poly (1,4-cyclohexanedimethanol terephthalate) (PCT), polypropylene terephthalate (PPT), polybutylene naphthalate (PBN), and liquid crystal polymers (LCPs) such as, for example the VECTRA® brand LCP (Hoechst Celanese Corporation, Somerville, NJ). Still other suitable polyesters are copolyesters, for example, poly(1,4-cyclohexylene dimethylene terephthalate-coisophthalate), poly(ethylene terephthalate-co-ethylene naphthalate (PETN), and the like. PET and PBT are the most preferred due to their large availability as well as the fact that molding of such resins are well-known in the industry.
  • Blends of the above-listed polyesters may also be suitable for polyester compositions of this invention, including preferably blends of two of such polyesters. Blends of three or more polyesters can be used. Such two component blends are formed by a ratio of between about 5 to 50 % by weight of the total blend. For example, a preferred blend useful in this invention is a ratio of between 5 to about 25% PET and about 75 to about 95% PBT, absent other ingredients.
  • Additionally, such polyester resins or resin blends can contain minor amounts of other polymeric materials, such as polycarbonates, polyphenylene sulfide, polyarylate, polyamide and the like and mixtures thereof.
  • Preferably these polyesters or co-polyesters are characterized by inherent viscosities of at least 0.4 as measured by ASTM D-2857, and no higher than about 1.4. The modifier composition components (b) and (c) of this invention are very useful with PET alone.
  • Also as part of the polyester resin of the polyester composition are conventional additives known to the art. Some of them include, for example, antioxidants, stabilizers, lubricants, nucleating agents, colorants, mold release agents, ultraviolet light stabilizers, and the like. Examples of suitable antioxidants include phosphites. Examples of suitable stabilizers include bis-phenol A based epoxy. Examples of suitable lubricants include olefinic waxes. Examples of suitable nucleating agents include sodium salts. Additives which improve physical properties can also be employed including those which improve tensile strength or the other physical characteristics desirable in such resins. Some of these characteristics are listed in Table 1 below. These additives are present in relatively minor amounts and do not unduly affect the desired characteristics of the finished products. Generally, the additives are present in an amount of between about 1 to about 5% of the total composition.
  • A separate and optional component of the polyester composition is a flame retardant composition or package used at a conventional level. Generally, such flame retardant compositions include a bromine containing compound (such as brominated polycarbonate, decabromodiphenyloxide, brominated acrylic, brominated polystyrene, etc.). Such compounds are available commercially, such as from Ethyl Chemical Corp., Great Lakes Chemical Corp., Dead Sea Bromine Co., etc. Also part of the flame retardant package is a synergist, typically e.g., antimony oxide, zinc oxide, and sodium antimonate, among others known to the art. Still a third component of the flame retardant composition is a drip suppressant, such as asbestos, teflon and the like. Suitable flame retardant compositions are known to the art and the selection of the components thereof does not limit the present invention. If a flame retardant composition is present in the polyester composition of this invention, it is present in a percentage by weight of the total composition of between 0 to about 20%.
  • In addition to the impact modifier composition components which are discussed in detail above, the total polyester composition may include reinforcing agents or fillers. Generally, such reinforcing agents or fillers may be present in the total composition between about 0 to about 50% by weight of the total composition.
  • Thermally stable reinforcing agents or reinforcing fibers used in the invention may be any such agents or fibers which are thermally stable at the conditions normally used in the production of products from polyester molding compositions. Suitable reinforcing agents include, for example, glass fiber, asbestos fiber, carbon fiber, ceramic fiber, fibrous potassium titanate, iron whiskers, and the like. Glass is the most preferred. While fiber is the most preferred form for the reinforcing agent, other suitable forms may also be employed in the practice of the invention. Where reinforcing fibers are used, such fibers should normally have diameters between about 5 and about 30 microns, typically from 10-21 µm, and preferably from 11-16 µm. Aspect ratios (ratio of length of fiber to diameter of fiber) are desirably at least about 5. The reinforcing fiber typically has a length of generally from 1-10 mm, preferably from 2-6 mm and more preferably from 3-5 mm. Glass fibers, where used, preferably have diameters between about 10 and about 15 microns and aspect ratios of at least about 20.
  • The reinforcing agent/fiber is employed in the polyester composition generally in the range of about 3 to about 50 weight percent based on total weight of the total polyester composition, typically 10-35 weight percent, and preferably 10-30 weight percent. As is commonly recognized, the use of such reinforcing agents/fibers improves substantially such physical properties as tensile strength, flexural strength, flexural modulus and heat distortion temperature of the polyester composition.
  • Glass or other fibers/agents for use in the invention may be manufactured and incorporated into the composition in any suitable manner, such as by separate extrusion blending with the polyester resin, extrusion blending with other ingredients of the compositions of the invention or incorporating into the resin or polyester composition during injection molding of products from the polyester composition.
  • Suitable fillers include, but are not limited to, mica, talcum, clay, titanium dioxide and the like. There may be variants within the same filler type such as, for example, the muscovite type mica (supplied by KMG, Inc.), the phlogopite type mica (Suzorite, Inc.) and the like. The size of the filler particles is in the general range of 20-500 µm, typically in the range 30-100 µm and preferably 40-60 µm. The filler is employed in the polyester composition, generally in the range 5-35 weight percent, typically 7-25 weight percent, and preferably 10-20 weight percent.
  • In one presently preferred embodiment, a polyester composition of the present invention contains about 61.5% by weight of the total composition of PET with about 3.5% additives. About 16% by weight of the total composition is the copolymer ethylene/methyl acrylate. About 4% by weight of the total composition is the terpolymer ethylene/methyl acrylate/glycidyl methacrylate. Finally, about 15% by weight of the total composition is fiberglass. This composition is characterized by a notched Izod impact strength of about 186.8 J/m (3.5 ft-lb/in).
  • As will be obvious to those of skill in the art, other polyester compositions falling within this description can be readily prepared by resort to the teachings herein. Useful compositions may have a variety of characteristics, depending on the use to which the molding polyester composition is put. The primary characteristic of the composition is a good notched or unnotched Izod impact strength (ASTM D-256). Generally, the higher the Izod measurement, the better. However, other characteristics which are important in the use of these molding compositions are tensile strength, break elongation and tensile modulus, as measured by ASTM D-638; viscosity measured in shear rate of 1000 sec-1 at 280°C, flex stress and flex modulus (ASTM D-790) and heat deflection temperature (ASTM D-648). Such characteristics are conventional in the art.
  • Generally, the polyester compositions of this invention are useful in the preparation of molded articles of manufacture, including without limitation, automobile panels, automobile parts, industrial plumbing and other construction parts.
    • III. Methods of Preparing the Modifier Compositions, the Polyester Compositions and the Molded Articles.
  • The polyester compositions of this invention are prepared by resorting to conventional methods. The impact modifier composition may be prepared by first dry mixing the components. For example, with regard to the impact modifier composition itself, the co-polymers and terpolymers may simply be blended or dry mixed at any convenient speeds and at room temperature.
  • Thus, the impact modifier composition components may be combined and sold as a physical or mechanical blend for addition to the polyester resin during manufacture of the polyester composition.
  • Alternatively, the individual components of the modifier composition may be dry mixed directly with the components of the polyester resin. The other ingredients of the polyester composition may also be added.
  • In preparing molded compositions of the invention, the reinforcing fibers may be intimately blended into the polyester resin by any suitable means such as by dry blending or melt blending, blending in extruders, heated rolls or other types of mixers, etc. Conventional master batching techniques may also be used. The same considerations apply to addition of the other essential or optional ingredients of the composition of the invention, including specifically an inert filler of low aspect ratio, the reinforcing agents, the polyester compositions, etc. Suitable blending and molding techniques are well known in the art and need not be described in detail herein.
  • The extrusion may be carried out in a suitable extruder such as for example a twin screw extruder with down-stream feeding capability. Many such extruders are commercially available such as, for example, the 40 mm Werner Pleiderer twin screw extruder. The extruder may be fed with the resin and additives stated above at the main feeder while the glass is fed downstream. The machine temperature is kept at a suitable level above the melting point of the selected polyester(s). For PET, for example, the temperature may range 260-300°C. The material is compounded and then extruded into a suitable shape such as, for example, pellets. The pellets may then be injection molded into suitable parts.
  • In a preferred embodiment of the invention, the polyester composition of the invention is compounded by dry blending the polyester resin, the reinforcing agent and/or filler and the impact modifier composition, followed by melt mixing in an extruder at a temperature which exceeds the melting point of the polyester resin, i.e., with barrel temperatures between about 260 and about 300°C. Likewise, in molding products of the invention from molding polyester compositions of the invention; injection molding is preferred. When injection molding is used, barrel temperatures between about 260 and 290°C are preferred. In a preferred embodiment, the molding polyester composition of the invention is formed by extrusion and pelletized. Products of the invention are then produced by injection molding the pelletized extrudate.
  • In still another alternative, the individual components of the modifier composition may be added to the extruder separately from the polyester resin and other components of the polyester composition. The components may be blended into the molten mixture prior to cooling. There are a number of alternative manufacturing steps which can be employed with the compositions of this invention. Such manufacturing steps are intended to be encompassed in this invention, as they are routine to one of skill in the art in the preparation of such compositions.
  • Finally, the polyester compositions of this invention containing the impact modifier compositions, when obtained by the end user, may be dried by any convenient method, remelted and molded into a number of industrially useful products, as described above.
  • The following examples illustrate the preferred compositions and methods of the invention. These examples are illustrative only and do not limit the scope of the invention. All percentages are by weight, unless otherwise indicated.
    • EXAMPLE 1: COMPARISON OF IMPACT MODIFIER COMPOSITIONS
  • In the following studies, a variety of impact modifier compositions or components thereof were studied in a polyester composition which consisted of polyethylene terephthalate and conventional additives, and 15% fiberglass as a reinforcing agent. The indicated modifier composition was incorporated at percentages indicated in column 1 of each of,Table 1 and Table 2.
  • For the purposes of the data reported in Tables 1 and 2, standard ASTM tests were conducted on the polyester composition. For example, viscosity was reported at a shear rate of 1000 sec-1; tensile stress and flex stress are reported in MPa (kpsi), break elongation is reported in percentage; tensile modulus and flex modulus are reported in GPa (mpsi), notched Izod and unnotched Izod impact results are reported as J/m (ft-lb/in.), heat deflection temperature (i.e., deflection temperature under load) is reported at 1.818 MPa (264 psi) and reported in °C and at 0.455 MPa (66 psi) reported in °C2. These characteristics are tested using the ASTM test designations identified above.
  • The following components are used in the Tables 1-2 below. COMPONENT A represents a commercial composition of ethylene ethylacrylate (Union Carbide). COMPONENT B represents a terpolymer of ethylene/methyl methacrylate /glycidyl methacrylate with a high (i.e., greater than 5% by weight) epoxy (glycidyl) level (Elf Atochem). COMPONENT C is a terpolymer of ethylene/methyl methacrylate /glycidyl methacrylate with a low (i.e., less than 5% by weight) epoxy (glycidyl) level (Elf Atochem). COMPONENT D is a 70%/30% ethylene/methyl acrylate copolymer with a melt index lower than 5. Suitable copolymers are marketed by Elf Atochem.
    Figure 00240001
    Figure 00250001
    Figure 00260001
  • As illustrated in the data reported in Table 1 above, individual copolymers (A and D) and terpolymers (B and C) useful in the present invention, when used alone at the 5% level as impact modifiers, produced Izod impacts similar to commercial PETs. For example, for components A through D when used at a level of 5% as impact modifiers in the PET composition, the notched Izod impact measurements ranged between 1.10 to 1.92. The unnotched Izod impact measurements range between 5.0 to 9.3 for these same compositions.
  • Comparing results of Tables 1 and 2, Component B, when raised from 5% (Table 1) to 20% by weight (Table 2) as the impact modifier, produced an increase in notched Izod measurement from 102.5 to 263.8 J/m (1.92 to 4.94 ft-lb/n), and in unnotched Izod from 497 to 1084 J/m (9.3 to 20.3 ft-lb/n). Component C, when raised from 5% (Table 1) to 20% by weight (Table 2) as the impact modifier, produced an increase in notched Izod measurement from 75.8 to 144.2 J/m (1.42 to 2.70 ft-lb/n), and in unnotched Izod from 363 to 769 J/m (6.8 to 14.4 ft-lb/n). Component D alone as impact modifier when raised from 5% (Table 1) to 20% by weight (Table 2) in the composition produced no or little appreciable change in notched Izod (66.7 to 69.4 J/m) (1.25 to 1.3 ft-lb/in) or unnotched Izod measurement (347 to 427 J/m) (6.5 to 8.0 ft-lb/in).
  • Thus, it appears that Components B and C are good impact modifiers when used alone, but Component D is not an effective impact modifier when used alone in polyester.
  • Surprisingly, then, and in accordance with the present invention, an impact modifier composition containing Component B and Component D produced the best results in the PET composition of the experiment. The good results appear independent of the ratio of the two components to each other (see Table 2). In fact the best overall results, taking into account the other test results as well as Izod measurements, are provided by the impact modifier composition containing 4% terpolymer B and 16% copolymer D. Another good impact modifier composition contains 14% by weight terpolymer B and 6% by weight co-polymer D.
    • EXAMPLE 2: OTHER POLYESTER RESINS
  • These examples demonstrate the use of another resin in the polyester compositions of the present invention.
  • A. The polyester composition tested contained a polyester resin of about 67.5% PBT and additives, and 7.5% by weight polycarbonate. The other components of the polyester composition included 12.5% by weight of the reinforcing agent glass fiber, 2.5 % by weight of the filler, glass flake and 10% by weight of the indicated modifier or modifier composition. The impact modifiers tested included COMPONENT A of Example 1, the Rohm and Haas core shell modifier marketed under the trademark EXL2330, and a modifier composition according to the present invention comprised of 3.3% COMPONENT B and 6.7% COMPONENT D of Example 1. Table 3 shows Izod measurements which were reported in the ISO Izod tests in kilojoules per square meters.
    Modifier Notched Izod Unnotched Izod
    10% A 7.4 31
    10% EXL2330 7.9 33
    3.3%B/6.7%D 11.2 45
    The results demonstrate that the impact modifier composition of the present invention is effective in a PBT/polycarbonate resin-containing polyester composition.
  • B. The polyester composition tested contained a polyester resin of about 80% by weight PBT and conventional additives, no filler, no reinforcing agent, and 20% by weight of the indicated modifier or modifier composition. The impact modifier compositions of the invention tested included 12% COMPONENT B/8% COMPONENT D of Example 1, and 4% COMPONENT B and 16% COMPONENT D of Example 1. The ISO Izod measurements are reported in Table 4 in kilojoules/meter as described immediately above, but in this case are reported at three different temperatures, room temperature (RT), -20°C and -40°C. Room temperature impact of PBT alone would be at most 5.5 (ISO method).
    Modifier Notched Izod Impact at
    RT -20°C -40°C
    12%B/8%D No break 15 10
    4%B/16%D 18 16 10
    This data also shows that modification of impact occurs similarly in a polyester resin matrix other than PET.
  • C. Various other compositions containing glass reinforcing agent components ranges from 0 to 30% by weight in a PET composition using the 4%B/16%D modifier composition have preliminarily provided data demonstrating good impact in the final polyester composition as measured in the ISO Izod tests.
  • All references and patents cited above are incorporated herein by reference. Numerous modifications and variations of the present invention are included in the above-identified specification and are expected to be obvious to one of skill in the art. Such modifications and alterations to the compositions and processes of the present invention are believed to be encompassed in the scope of the claims appended hereto.

Claims (23)

  1. A polyester composition having improved characteristics of impact resistance comprising:
    (a) between 40% and 90% by weight of the total composition of a polyester resin containing a polyester and between 1% and 5% by weight of the total composition of additives;
    (b) between 5% to 25% by weight of the total composition of a component selected from the group consisting of an ethylene alkyl acrylate copolymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10;
    (c) between 5% to 25% by weight of the total composition of a component selected from the terpolymer group consisting of ethylene/alkylacrylate/glycidyl methacrylate; ethylene/alkyl acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate, wherein said alkyl is C1 to C10;
    (d) from 3% to 50% by weight of the total composition of a reinforcing agent; and
    (e) from 0% to 20% by weight of the total composition of a flame retardant composition.
  2. The composition according to claim 1
    wherein said polyester resin contains a compound selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate; polybutylene naphthalate and blends thereof.
  3. The composition according to claim 1,
    wherein the total amount of the components (b) and (c) does not exceed 40% by weight of the total weight of the composition of claim 1.
  4. The composition according to claim 1
    wherein said component (b) is an ethylene/methyl acrylate copolymer.
  5. The composition according to claim 1
    wherein the component (c) is an ethylene/methyl acrylate/glycidyl methacrylate.
  6. The composition according to claim 1
    wherein said reinforcing agent is selected from the group consisting of glass beads; glass flakes; fiberglass, asbestos fibers, mica, talc, carbon fiber, and steel fiber.
  7. The composition according to claim 2
    wherein said blends comprise at least two of said polyesters in a weight ratio of between 5% to 50% of the total weight of the combined polyesters.
  8. The composition according to claim 1
    wherein the copolymer of component (b) comprises at least 30% by weight of the alkyl acrylate or alkyl methacrylate
  9. The composition according to claim 1
    wherein the terpolymer of component (c) comprises between 1 to 15% by weight of the glycidyl acrylate or glycidyl methacrylate and between 1% to 40% by weight of the alkyl acrylate or alkyl methacrylate.
  10. The composition according to claim 1 comprising:
    (a) about 61.5% by weight of the total composition of a polyethylene terephthalate polyester composition, said composition containing about 3.5 % by weight additives;
    (b) about 16% by weight of the total composition of ethylene/methyl acrylate;
    (c) about 4% by weight of the total composition of terpolymer ethylene/methyl acrylate/glycidyl methacrylate; and
    (d) about 15% by weight of the total composition of fiberglass.
  11. The composition according to claim 1
    wherein said additives comprise lubricants, stabilizers, antioxidants, stabilizers, nucleating agents, colorants, mold release agents, ultraviolet light stabilizers.
  12. An article of manufacture molded from the polyester composition of claim 1.
  13. Use of an acrylic modifier composition comprising:
    (a) between 10% to 90% by weight of a first component selected from the group consisting of an ethylene alkyl acrylate co-polymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10; and
    (b) between 10% to 90% by weight of a second component selected from the terpolymer group consisting of ethylene/alkylacrylate/ glycidyl methacrylate; ethylene/alkyl acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate,
    wherein said alkyl is C1 to C10; for improving impact resistance of reinforced polyester compositions.
  14. The use according to claim 13
    wherein said component (a) is an ethylene/methyl acrylate copolymer.
  15. The use according to claim 13
    wherein the component (b) is an ethylene/methyl acrylate/glycidyl methacrylate.
  16. The use according to claim 13
    wherein the copolymer of component (a) comprises at least about 30% by weight of the alkyl acrylate or alkyl methacrylate.
  17. The use according to claim 13
    wherein the terpolymer of component (b) comprises between 1 to 15% by weight of the glycidyl acrylate or glycidyl methacrylate and between 1% to 40% by weight of the alkyl acrylate or alkyl methacrylate, with the balance being ethylene.
  18. A reinforced polyester composition containing at least 10% by weight of the composition of the acrylic modifier composition defined in claim 13.
  19. An article of manufacture molded from the polyester composition of claim 18.
  20. A method for increasing the strength and impact resistance of polyester compositions comprising adding to a reinforced polyester resin a modifier composition defined in claim 13.
  21. The method according to claim 20 further comprising the steps of:
    (a) melting between 40% and 90% by weight of the total composition of a polyester resin and between 1% and 5% by weight of the total composition of additives at a temperature in excess of the melting temperature of said polyester in an extruder;
    (b) adding to the composition of step (a) a modifier composition comprising between 10% to 90% by weight of a first component selected from the group consisting of an ethylene alkyl acrylate copolymer and ethylene alkyl methacrylate copolymer, wherein said alkyl is C1 to C10; and between 10% to 90% by weight of a second component selected from the terpolymer group consisting of ethylene/alkylacrylate/glycidyl methacrylate; ethylene/alkyl acrylate/glycidyl acrylate; ethylene/alkyl methacrylate/glycidyl acrylate; and ethylene/alkyl methacrylate/glycidyl methacrylate, wherein said alkyl is C1 to C10;
    (c) adding to the composition of step (b) a reinforcing agent; and/or
    (d) adding to the composition of step (c) a reinforcing agent;
    (e) extruding the molten composition resulting from steps (a) through (d) from said extruding apparatus, wherein said composition extrudes as an intimate mixture;
    (f) subjecting said mixture of step (e) to means to decrease the temperature thereof and solidify said mixture; and
    (g) subjecting said solid composition of step (f) to means to reduce its size.
  22. The method according to claim 21 wherein said steps (a) through (d) are performed simultaneously.
  23. The method according to claim 21 wherein said steps (a) through (d) are performed sequentially.
EP97117911A 1996-10-23 1997-10-16 Method and compositions for toughening polyester resins Expired - Lifetime EP0838501B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US740006 1991-08-02
US08/740,006 US6020414A (en) 1996-10-23 1996-10-23 Method and compositions for toughening polyester resins

Publications (3)

Publication Number Publication Date
EP0838501A2 EP0838501A2 (en) 1998-04-29
EP0838501A3 EP0838501A3 (en) 1998-06-17
EP0838501B1 true EP0838501B1 (en) 2002-12-04

Family

ID=24974676

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97117911A Expired - Lifetime EP0838501B1 (en) 1996-10-23 1997-10-16 Method and compositions for toughening polyester resins

Country Status (7)

Country Link
US (1) US6020414A (en)
EP (1) EP0838501B1 (en)
JP (1) JPH10152607A (en)
KR (1) KR19980033011A (en)
CN (1) CN1182101A (en)
CA (1) CA2218856A1 (en)
DE (1) DE69717584T2 (en)

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255906A (en) * 1998-03-13 1999-09-21 Elf Atochem Japan Kk Production of modified polyester molding and the molding
US6020432A (en) * 1998-07-02 2000-02-01 Hna Holdings, Inc. High density polyester composition
WO2000015717A1 (en) * 1998-09-14 2000-03-23 Eastman Chemical Company Polyester compositions containing an impact modifier
WO2000015716A2 (en) * 1998-09-14 2000-03-23 Eastman Chemical Company High impact polyester blends
NL1012176C2 (en) * 1999-05-28 2000-11-30 Dsm Nv Halogen-free fire retardant composition.
US6277905B1 (en) * 1999-09-23 2001-08-21 Eastman Chemical Company Process for improving the toughness of PCT formulations by adding rubber impact modifiers
FR2801598B1 (en) 1999-11-26 2005-03-11 Atofina COMPOSITIONS OF THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES
FR2801596B1 (en) * 1999-11-26 2004-12-03 Atofina THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES AND SHOCK MODIFIER COMPOSITIONS
FR2801597B1 (en) 1999-11-26 2005-03-11 Atofina COMPOSITIONS OF THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES
US6814905B1 (en) 1999-12-02 2004-11-09 Associated Packaging Enterprises, Inc. Continuous process and apparatus for making thermoformed articles
US6576309B2 (en) * 1999-12-02 2003-06-10 Associated Packaging Enterprises Thermoplastic compositions having high dimensional stability
JP2002047397A (en) * 2000-07-31 2002-02-12 Kanegafuchi Chem Ind Co Ltd High rigidity thermoplastic polyester resin composition with good mold surface transfer
US7015261B1 (en) * 2000-11-17 2006-03-21 Arkema Inc. Impact modifier combination for polymers
EP1208958B1 (en) * 2000-11-28 2006-01-18 Associated Packaging Enterprises, Inc. Continuous thermoforming process and apparatus for making articles
US6773735B1 (en) 2000-11-28 2004-08-10 Associated Packaging Enterprises, Inc. Multi-layered thermoplastic container
US7759449B2 (en) * 2000-12-15 2010-07-20 Wellman, Inc. Methods for introducing additives into polyethylene terephthalate
US6500890B2 (en) * 2000-12-15 2002-12-31 Wellman, Inc. Polyester bottle resins having reduced frictional properties and methods for making the same
US20030039783A1 (en) * 2001-03-30 2003-02-27 Stafford Steven Lee Polyesters and polyester containers having a reduced coefficient of friction and improved clarity
USH2132H1 (en) 2001-06-29 2005-11-01 Eastman Chemical Company Polyester containers having a reduced coefficient of friction
US6986864B2 (en) * 2002-04-30 2006-01-17 David Scott Porter Polyester compositions
JP2004176906A (en) * 2002-09-30 2004-06-24 Tokai Rubber Ind Ltd Fuel system hose
AU2003275702A1 (en) * 2002-10-29 2004-05-25 Kaneka Corporation Thickener for thermoplastic polyester resin, thermoplastic polyester resin composition containing the same, and molded object obtained therefrom
KR20050037854A (en) * 2003-10-20 2005-04-25 에스케이씨 주식회사 Flame-retardant polyester film
US7834092B2 (en) 2003-12-12 2010-11-16 E. I. Du Pont De Nemours And Company Article comprising poly(hydroxyalkanoic acid)
PL1992662T3 (en) 2004-06-08 2011-01-31 Lanxess Deutschland Gmbh Moldable resins based on thermoplastic polyesters with improved flowability
US20060009556A1 (en) * 2004-07-08 2006-01-12 Mengshi Lu High gloss PET molding composition and articles made therefrom
US20060025510A1 (en) * 2004-08-02 2006-02-02 Dean David M Flame retardant polymer blend and articles thereof
US20070299212A1 (en) * 2005-02-03 2007-12-27 Smillie Benjamin A Polymer impact modifier blend concentrate
CN101155873A (en) * 2005-03-08 2008-04-02 因维斯塔技术有限公司 Polyester composition with high dimensional stability
DE102006006167A1 (en) * 2005-04-06 2006-10-12 Lanxess Deutschland Gmbh Molding compounds based on a thermoplastic polycarbonate
DE102005050957A1 (en) 2005-10-25 2007-04-26 Lanxess Deutschland Gmbh Thermoplastic moulding material for use, e.g. in electrical, motor, computer or domestic appliance industries, comprises thermoplastic polyester and olefin-alkyl (meth)acrylate copolymer with high melt flow index
US7935737B2 (en) * 2006-01-27 2011-05-03 Sabic Innovative Plastics Ip B.V. Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)
US7923506B2 (en) * 2006-01-27 2011-04-12 Sabic Innovative Plastics Ip B.V. Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)
US8680167B2 (en) * 2006-01-27 2014-03-25 Sabic Innovative Plastics Ip B.V. Molding compositions containing fillers and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)
US8304495B1 (en) 2006-02-01 2012-11-06 E I Du Pont De Nemours And Company Articles comprising polyester and ethylene copolymer
KR20080094807A (en) * 2006-02-01 2008-10-24 이 아이 듀폰 디 네모아 앤드 캄파니 Articles Including Polyester and Ethylene Copolymers
FR2902434B1 (en) * 2006-06-16 2008-08-01 Arkema France POLYLACTIC ACID COMPOSITION HAVING ENHANCED SHOCK RESISTANCE
US7799838B2 (en) * 2006-07-26 2010-09-21 Sabic Innovative Plastics Ip B.V. Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom
US8309656B2 (en) 2006-07-26 2012-11-13 Sabic Innovative Plastics Ip B.V. Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom
US8034522B2 (en) * 2006-11-13 2011-10-11 Reichhold, Inc. Polyester toner resin compositions
US20080118729A1 (en) * 2006-11-16 2008-05-22 General Electric Company Thermoplastic composition, method of making, and articles formed therefrom
US8058360B2 (en) 2007-06-01 2011-11-15 Grupo Petrotemex, S.A. De C.V. Polyester blends exhibiting low temperature toughness
US20090069489A1 (en) * 2007-09-12 2009-03-12 Peter Vollenberg Polycarbonate-poly(ester-ether) copolymer composition, method of manufacture, and articles therefrom
US20090186966A1 (en) * 2008-01-22 2009-07-23 Sabic Innovative Plastics Ip B.V. Thermoplastic polyestercarbonate composition
WO2009094362A1 (en) * 2008-01-24 2009-07-30 E. I. Du Pont De Nemours And Company Toughened poly(trimethylene terephthalate) composition with reduced melt viscosity
CN102007182B (en) * 2008-04-16 2013-03-27 纳幕尔杜邦公司 Poly(hydroxyalkanoic acid) compositions toughened with ethylene alkyl acrylates
US9289795B2 (en) 2008-07-01 2016-03-22 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US20100015456A1 (en) * 2008-07-16 2010-01-21 Eastman Chemical Company Thermoplastic formulations for enhanced paintability toughness and melt process ability
CN101724235B (en) * 2008-10-17 2012-06-13 普立万聚合体（上海）有限公司 Biodegradable polyhydroxyalkanoate blend
US20110244241A1 (en) * 2010-03-08 2011-10-06 Aditya Ranade Adhesion in ectfe/polyester co-extruded structures using tie layers
US8734909B2 (en) * 2010-03-10 2014-05-27 Eastman Chemical Company Methods and apparatus for coating substrates
US9321549B2 (en) * 2010-03-22 2016-04-26 Clear Lam Packaging, Inc. Biopolymer roll stock for form-fill-sealed article
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
CN104812849A (en) * 2012-12-04 2015-07-29 沙特基础全球技术有限公司 Coating system for coated metal or polymeric tube
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
JP2015205987A (en) * 2014-04-21 2015-11-19 東レ株式会社 Water section member
CN107667145B (en) * 2015-05-26 2020-06-30 Sabic环球技术有限责任公司 Poly(butylene terephthalate) compositions and related articles
CN109867919A (en) * 2017-12-04 2019-06-11 广州汽车集团股份有限公司 Polyethylene terephthalate composite material, product and preparation method
EP3775042A1 (en) * 2018-04-10 2021-02-17 SHPP Global Technologies B.V. High modulus ductile thermoplastic compositions having transparency to radio frequency signals
EP3712209A1 (en) * 2019-03-21 2020-09-23 SABIC Global Technologies B.V. High stiff thermoplastic compositions for thin-wall structures
CN110669320A (en) * 2019-08-26 2020-01-10 天津柯文实业股份有限公司 Preparation method of high-impact-resistance high-low-temperature-resistance poly (p-xylylene glycol terephthalate)
KR20220069024A (en) * 2019-09-13 2022-05-26 다우 글로벌 테크놀로지스 엘엘씨 Compatibilized Polymeric Compositions for Fiber Optic Cable Elements
CN112679917B (en) * 2020-12-09 2022-11-25 中广核瑞胜发（厦门）新材料有限公司 Cold-heat-resistant high-strength high-toughness PBT (polybutylene terephthalate) composite material suitable for full-shading lamp and preparation and application thereof
CN114889174B (en) * 2022-03-10 2024-11-22 珠海万通特种工程塑料有限公司 A LCP film and its preparation method and application
KR20230136986A (en) * 2022-03-21 2023-10-04 롯데케미칼 주식회사 Thermoplastic resin composition and article produced therefrom
CN115536977B (en) * 2022-10-21 2025-09-23 上海金山锦湖日丽塑料有限公司 ABS material suitable for outdoor use and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US32334A (en) * 1861-05-14 Moses ducharme
DE2345458A1 (en) * 1958-07-22 1975-03-20 Basf Ag MOLDING COMPOUNDS BASED ON POLYBUTYLENE TEREPHTHALATE
US3368995A (en) * 1965-08-03 1968-02-13 Teijin Ltd Fiberglass reinforced polyethylene terephthalate
GB1241168A (en) * 1967-08-29 1971-07-28 Ici Ltd Polyethylene terephthalate moulding compositions
US3953394A (en) * 1971-11-15 1976-04-27 General Electric Company Polyester alloys and molding compositions containing the same
US4122061A (en) * 1976-12-23 1978-10-24 General Electric Company Impact modified polyester compositions
US4140670A (en) * 1977-07-11 1979-02-20 Gaf Corporation PBT Injection molding composition
USRE32334E (en) 1978-02-28 1987-01-20 E. I. Du Pont De Nemours And Company Molding resins
JPS5592758A (en) * 1978-11-06 1980-07-14 Toray Ind Inc Resin composition
JPS55139448A (en) * 1979-04-17 1980-10-31 Toray Ind Inc Thermoplastic polyester composition for molding
US4320045A (en) * 1979-12-17 1982-03-16 Owens-Corning Fiberglas Corporation Polyester-based molding compositions
JPS56136856A (en) * 1980-03-31 1981-10-26 Dainippon Ink & Chem Inc Powder coating resin composition
US4444931A (en) * 1980-08-06 1984-04-24 Celanese Corporation Polyester blends
US4369280A (en) * 1981-08-04 1983-01-18 General Electric Company Polybutylene terephthalate molding compositions and articles molded therefrom
NL8204205A (en) * 1982-10-29 1984-05-16 Dsm Resins Bv POLYESTER AND ITS USE IN POWDER COATED.
US4891406A (en) * 1983-08-08 1990-01-02 Huels Aktiengesellschaft High impact strength molding compositions based on polyalkylene terephthalates
EP0148743B1 (en) * 1984-01-06 1991-04-10 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin composition
DE3403576A1 (en) * 1984-02-02 1985-08-08 Basf Ag, 6700 Ludwigshafen ELASTOMERIC THERMOPLASTIC MOLDS AND THEIR PRODUCTION
JPS61501270A (en) * 1984-02-24 1986-06-26 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Reinforced thermoplastic polyester composition
JPH0726008B2 (en) * 1987-03-31 1995-03-22 住友化学工業株式会社 Method for producing thermoplastic resin composition
CA1330129C (en) * 1987-06-16 1994-06-07 Nippon Oil & Fats Co., Ltd. Thermoplastic resin composition and method for preparing the same
US4900788A (en) * 1987-12-14 1990-02-13 E. I. Du Pont De Nemours And Company Blow molding polyester compositions
FR2625215B1 (en) * 1987-12-23 1990-04-27 Charbonnages Ste Chimique THERMOPLASTIC COMPOSITIONS BASED ON SATURED POLYESTER AND MOLDED ARTICLES CONTAINING SAME
JPH01247454A (en) * 1988-03-29 1989-10-03 Nippon Petrochem Co Ltd polyester resin composition
US5483001A (en) * 1988-03-30 1996-01-09 Norsolor Thermoplastic compositions based on ethylene polymer and polyester
FR2629465B1 (en) * 1988-03-30 1992-02-21 Norsolor Sa FLEXIBLE THERMOPLASTIC COMPOSITIONS BASED ON ETHYLENE COPOLYMER AND SATURED POLYESTER AND ARTICLES CONTAINING THEM
JPH0660246B2 (en) * 1988-10-07 1994-08-10 住友電装株式会社 Resin molding method and molded body
JPH03122158A (en) * 1989-10-06 1991-05-24 Nippon Petrochem Co Ltd Polyester resin compositon
JP2886951B2 (en) * 1990-07-30 1999-04-26 三井化学株式会社 Dry toner binder
JP2914745B2 (en) * 1990-10-12 1999-07-05 三井化学株式会社 Resin composition for powder coating
IT1243744B (en) * 1990-10-16 1994-06-21 Enichem Spa POLYMERIC ALLOYS BASED ON POLYETHYLENE TEREPHALATE AND HIGH DENSITY POLYETHYLENE WITH HIGH IMPACT RESISTANCE.
JPH05112703A (en) * 1991-03-08 1993-05-07 Nippon Petrochem Co Ltd Polyester resin composition
IT1250738B (en) * 1991-08-02 1995-04-21 Donegani Guido Ist THERMOPLASTIC COMPOSITIONS WITH HIGH TENACITY AND IMPACT RESISTANCE
US5344912A (en) * 1992-02-03 1994-09-06 Therma-Plate Corporation Elevated temperature dimensionally stable polyester with low gas permeability
US5321056A (en) * 1992-06-19 1994-06-14 Rohm And Haas Company Amorphous, aromatic polyester containing impact modifier
JP3366750B2 (en) * 1993-11-18 2003-01-14 帝人株式会社 Polyester resin composition
AU663661B1 (en) * 1994-06-03 1995-10-12 Morton International, Inc. Impact-resistant acrylic powder coatings
US5554120A (en) * 1994-07-25 1996-09-10 Advanced Cardiovascular Systems, Inc. Polymer blends for use in making medical devices including catheters and balloons for dilatation catheters
US5849846A (en) * 1994-07-25 1998-12-15 Advanced Cardiovascular Systems, Inc. Balloons for medical catheters
US5510454A (en) * 1995-01-20 1996-04-23 E. I. Du Pont De Nemours And Company Production of poly(ethylene terephthalate)

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
English translation of JP-A-1247454 *

Also Published As

Publication number Publication date
JPH10152607A (en) 1998-06-09
EP0838501A3 (en) 1998-06-17
DE69717584T2 (en) 2003-09-25
KR19980033011A (en) 1998-07-25
EP0838501A2 (en) 1998-04-29
MX9708125A (en) 1998-08-30
US6020414A (en) 2000-02-01
DE69717584D1 (en) 2003-01-16
CA2218856A1 (en) 1998-04-23
CN1182101A (en) 1998-05-20

Similar Documents

Publication Publication Date Title
EP0838501B1 (en) Method and compositions for toughening polyester resins
US6300399B1 (en) High specific gravity polyester blend
WO1998027159A1 (en) Tough reinforced polyesters with improved flow
US5436296A (en) Compositions of polymeric materials including polyalkylene terephthalates and polyethylene
US5091459A (en) Thermoplastic blow moldable polyethylene terephthalate compositions
JP3338330B2 (en) Polyester resin composite molding
US5061757A (en) High impact strength polyamide blends and method for preparation thereof
CA2489511C (en) Glass fiber filled thermoplastic compositions with good surface appearance
EP0322043B1 (en) Polyketone polymer composition
JPS60173056A (en) Resin composition
JPS59191758A (en) Polycarbonate resin composition
JPH01144447A (en) Glass fiber reinforced thermoplastic molding material based on polyester and graft polymer
US5068274A (en) Secondary amides in polyethylene terephthalate molding compositions
JP3040142B2 (en) Reinforced resin composition
JPH01225647A (en) Resin composition
JPH041260A (en) Polyester resin composition
JP2001514699A (en) Injection molded product of impact resistant polyester
JPH01167370A (en) thermoplastic resin composition
WO1991019767A1 (en) Thermoplastic blow moldable polyester compositions
CN101870795B (en) Thermoplasticity alloy composition
JPS62184051A (en) Resin composition
JP3017232B2 (en) Resin composition
JP3526077B2 (en) Polyester resin composition and molded article thereof
JP2583231B2 (en) Impact resistant polyester resin composition
JPH04146956A (en) Polybutylene terephthalate resin composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE ES FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17P Request for examination filed

Effective date: 19981023

AKX Designation fees paid

Free format text: DE ES FR GB

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR GB

17Q First examination report despatched

Effective date: 19990311

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69717584

Country of ref document: DE

Date of ref document: 20030116

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030627

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030905

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081014

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20081014

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20081015

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091102

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091016